DE2310649A1 - SELECTIVE HERBICIDAL AGENTS - Google Patents

Description

The invention relates to selective herbicidal compositions based on diurethanes, in particular for combating weeds in cotton crops.

The herbicidal effect of diurethanes is already known (German Offenlegungsschriften Nos. I.567.151 and I.568.621). However, these are predominantly selective herbicides for use in beet crops. A selectivity these herbicides do not have any effect on cotton plants.

The object of the present invention is to provide a weed control agent to create that can be used especially in cotton crops.

According to the invention, this object is achieved by means

which are characterized by a content of at least one

Compound of the general formula

0 - co -:

-NH-CO-X-R

409837/1093

-2- SCHERINGAG

Patent department

February 28, 1975

in the

R ₁ propyl, butyl, isobutyl or benzyl,

R _{2 is} phenyl or one or more times by methyl and / or ethyl

and / or chlorine and / or methoxy and / or methyl mercapto

substituted phenyl, R, methyl or ethyl and X oxygen or sulfur

mean.

The agents according to the invention are distinguished by a surprising great compatibility with cotton in every stage of development, the cultivated plants even in the seedling stage are not harmed by using the funds. But this means an extraordinary technical progress, because thus weed control in these crops regardless of their stage of development at any point in time can take place, which allows an optimal control of the existing weeds to be expected. One such possibility is offered by the Herbicides based on phenylureas previously used for weed control in cotton are not used until they are in a growth stage The cotton can be used, in which the weeds are already strongly developed and therefore difficult to control are.

The agents according to the invention develop the most favorable effect when they are used in the post-emergence process

40 9 8 37/1093

-j- SCHERINGAG

Patent department

February 28, 1973

will. The agents not only work against the weeds that have already emerged, but also because of their residual effect in the soil also against germinating weeds, so that long-term control success is guaranteed.

The agents according to the invention can be used except in cotton crops Also used in peanuts, rice and carrot crops for weed control, in which they are also exceptional are selectively effective.

The herbicidal effect of the agent extends against many types of weeds, of which z. B. The following are to be mentioned: Setaria verticillata, Amarantus spinosus, Datura stramonium, Portulaca oleracea, Xanthium pensylvanicum, Eleusine indica, Rottboellia exaltata, Sinapis sp., Solanum sp., Stellaria media, Senecio vulgaris, Lamium amplexicaule, Centaurea cyanus, Amarantus retroflexus, Galium aparine, Chrysanthemum segetum, Echlnochloa crus galli, Setaria italica, Ipomoea purpurea, Polygonum lapathifollum, Digitaria sanguinalis, Setaria faberi.

The application rates for selective weed control are about 0.5 to 5 kg active ingredient / ha. These application rates can be if necessary, increase up to 10 kg of active ingredient / ha without the useful plants being significantly impaired.

409837/1093

.4- SCHERINGAG

Patent department

February 28, 1973

The compounds to be used according to the invention can either be used alone, in a mixture with one another or in a mixture with others Active ingredients are used. If desired, others can Plant protection products or pesticides, e.g. B. fungicides, nematicides or other agents, depending on the one desired Purpose to be added. An addition of fertilizers is z. B. also possible.

If a broadening of the spectrum of activity is intended, other herbicides can also be added, although this is true the selectivity is not always retained depending on the nature of the mixture partner. Suitable herbicidally active mixing partners are, for. B. Active ingredients from the groups of carbamic acid and thiocarbamic acid esters, the substituted anilines and anilides, triazines, amino-triazoles, diazines, such as uracile, z. B. jJ-Cyclohexyl ^ jö-trimethyleneuracil, l-phenyl - ^ - amino-S-chlorpyridazon (6), aliphatic carboxylic acids and halocarboxylic acids, halogenated benzoic acids and phenylacetic acids, aryloxycarboxylic acids, Hydrazides, amides, nitriles, halocarboxylic acids, e.g. B. 2,2-dichloropropionic acid or its salts, tetrafluoropropionic acid or their salts, esters of such carboxylic acids, ureas, 2,5,6-trichlorobenzyloxypropanol, agents containing rhodan and other.

Depending on the intended use, other substances can also be added, among which z. B. also non-phytotoxic additives understand the synergistic effects of herbicides

-s- SCfIERINGAG

Patent department

February 28, 1973

Increase in performance can result, such as wetting agents, emulsifiers, solvents, oily additives and others.

The active compounds according to the invention are expediently in the form of preparations, such as powders, scattering agents, granules, solutions, Emulsions or suspensions, with the addition of liquid and / or solid carriers or * diluents, and optionally of wetting agents, adhesives, emulsifying agents and / or dispersing agents.

Suitable liquid carriers are, for. B. water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, and mineral oil fractions.

Mineral earths are suitable as solid carriers, e.g. B. Tonsil, silica gel, talc, kaolin, attaclay, limestone, silica and vegetable products, e.g. B. Flours.

The following surface-active substances should be mentioned: z. B. calcium lignin sulfonate, Polyoxyethylene octylphenol ether, naphthalenesulphonic acids, phenolsulphonic acids, formaldehyde condensates, fatty alcoholsulph ate and fatty acid alkali and alkaline earth salts.

It has surprisingly been found that the herbicidal effect and the selectivity of the agents can be increased if they contain the surfactants in excess of the usual Contain proportions exceeding quantities.

409837/1093

-6- SCHERINGAG

Patent department

February 28, 1975

The proportion of the active ingredient (s) in the various preparations can vary within wide limits. For example, the agents contain about 20 to 80 percent by weight of active ingredients, About 80 to 20 percent by weight of liquid or solid carrier substances and optionally up to 50 percent by weight of surface-active substances Fabrics.

The agents can be applied in the usual way, for example with water as the carrier in spray liquid quantities of 100 to 1000 liters / ha. For total weed control, required spray volumes of more than 1000 liters of Aia can be applied under certain circumstances. An application of the means in the so-called eUltra-low-Volume method is just as possible as their application in the form of so-called microgranules.

Pie._Production of these preparations can be known per se Way, e.g. B. by mixing or milling processes. If desired, the individual components can also only be mixed shortly before they are used, as is done in practice, for example, in the so-called tank mix process will.

The new compounds to be used according to the invention can be prepared by processes known per se. This is done e.g. B. by
a) Compounds of the general formula

... A 0 9 8 3 7 / V0.9.3L

-τ- SCHERINGAG

Patent department

February 28, 1973

. or their alkali salts with carbamoyl chlorides of general formula

^Χ ^> Ν - CO - Cl

optionally in the presence of a tertiary organic base, such as. B. triethylamine or pyridine, at temperatures lets react from 0 ° C to 100 ° C

or

b) compounds of the general formula

- CO - Cl

Ü-NH -CO-X-R with amines of the general formula

R ₂

in the presence of an acid acceptor, e.g. B. an inorganic Base, such as sodium hydroxide solution, sodium carbonate or potassium carbonate, or a tertiary organic base, such as triethylamine, implements

or

A09837 / t0a3

-β- SCHERINGAG

Patent department

28.

c) compounds of the general formula

catalytic, e.g. B. using nickel in methanol, hydrogenated to the corresponding amine and then compounds of the general formula Ver

R-X-CO-Cl

in the presence of an acid acceptor, e.g. B. an inorganic base such as sodium hydroxide solution, sodium carbonate or potassium carbonate, or an organic base such as triethylamine, converted to the desired process products and then isolated in the usual catfish, where R ₁ , R ₂ , R, and X have the above meaning .

The following examples explain the preparation of the compounds to be used according to the invention.

Methyl-N-C 1-4 -N-isobutyl-N-phenylcarbamoyloxy) -phenyl) -carbarnate

(Compound no. L) In a mixture of 14.9 g of N-isobutylaniline, 50 ml of water and ml of ethyl acetate, a solution of 22.9 6 chloroformic acid-5- (N-carbomethoxyamino) - is added with stirring at 10 to 15 ° C. phenyl ester in 50 ml of ethyl acetate and at the same time a solution

SCHERINGAG

Patent department

February 28, 1973

of 13.8 g of potassium carbonate in 50 ml of water was added dropwise. Stirring is continued for 30 minutes with ice cooling, then the organic
Phase separated and washed at 0 ° C with a little dilute sodium hydroxide solution and water. After drying with magnesium sulfate, the solution is concentrated under reduced pressure and pentane is added to the evaporation residue, whereupon the reaction product
crystallized out.

Yield: 23.3 g = 68 # of theory
Pp .: 128 to 129 ° C

Ethyl N- (3- (N-isobutyl-N-phenylcarbamoyloxy) phenyl) carbamate

(Connection no.2)

The sodium salt prepared from 16.7 β 3-hydroxycarbanilic acid methyl ester and sodium methylate (from 2.3 g sodium) in absolute methanol is suspended in 100 ml of dry methyl isobutyl ketone after the methanol has been thoroughly removed in vacuo. At 7O ⁰ C, a solution is, with stirring, 21.2 g of N-isobutyl-N-phenylcarbamoyl chloride in 50 ml of dry methyl isobutyl ketone is added dropwise and stirred for 45 minutes at this temperature. Then it is cooled to oil and at this temperature with little
diluted sodium hydroxide solution and water. After drying
with magnesium sulfate is evaporated under reduced pressure and the residue is treated with ether, whereupon the reaction product crystallizes out.

Yield: 23.1 g = 65 % of theory

Pp .: 100 to 101 ° C

The following compounds can be produced in an analogous manner. 409837/1093

SCHERINGAG Patent department

February 28, 1973

Connection no.

Name of the connection Physical
constant

Methyl N- [3- (N-n-butyl-N-phenylcarbamoyloxy) phenyl; carbamate

Ethy1-N- (3- (N-n-buty1-N-pheny1-carbamoyloxy) phenyl) carbamate

Methyl N- (3- (N-isobutyl-N- (3-methylphenyl) carbaraoyloxy) phenyl) carbamate

Ethyl N- (3- (N-isobutyl-N- (5-methylphenyl) carbamoyloxy) phenyl) carbamate

S-methyl-N- (3- (N-isobutyl-N - (> methylphenyl) carbamoyloxy) phenyl) thi oc arbamat

Methyl-N- (3- (N-phenyl-N-benzylcarbamoyloxy 3-phenyl) carbamate

S-methyl N- (3- (N-isobutyl-N-phenylcarbamoyloxy) phenyl) thiocarbamate

S-methyl-N- (3- (N-n-butyl-N-phenylcarbamoyloxy) phenyl) thiocarbamate

Methyl N- (3- (N-propyl-N-phenyl carbamoyloxy) phenyl) carbamate

Xthyl-N- (3- (N-propyl-N-phenylcarbamoyloxy ) -phenyl) - carbamate

S-methyl-N- (3- (N-propyl-N-phenylcarbamoyloxy ) -phenyl) -thiocarbamate

Methyl N - (> (N-n-butyl-N- (4-ethylphenylcarbamoyloxy) phenyl) carbamate

S-methyl-N- (3- (N-benzyl-N-phenylcarbamoyloxy) -phenyl) -thi oc arbamat

Xthyl-N- (3- (N-benzyl-N-phenylcarbamoyloxy) phenyl) carbamate Pp .: 82-85 ⁰ C.

- 1.5349

Pp .: 76-80 ° C

M.p .: 79-80 ° C

Mp .: 119-121 C Mp .: 83-86 ° C Mp .: 96-98 ° C Mp .: 83-85 ° C Mp .: 97-98 ⁰ C Mp .: 105-106 ° C Mp .: 94-96 ° C m.p .: 75-76 ° C m.p .: 129-131 ^W C m.p .: 83-85 ° C

409837/1093

-u- SCHERINGAG

PatmtabteHmg

28.

These compounds are readily soluble in acetone, cyclohexanone, ethyl acetate, isophorone, ether and tetrahydrofuran and are practical insoluble in water and light petrol.

Compounds No. 1, 2, 4, 7, 9, 10, 11, 12 and as selective herbicides in cotton, carrot, peanut and rice crops are particularly distinguished from the compounds according to the invention.

The following examples illustrate the invention. example 1

In the greenhouse, the plants listed below were post-emergence with application rates of jj kg Active ingredient / ha treated. The agents were used as emulsions in 5OO liters of water per hectare on those in the youth stage Plants applied. The evaluation takes place 14 days after the treatment by scoring according to the rating scale of 0 = ηtotal destroyed "up to 10 =" not damaged ".

The findings show the far better selectivity and weed effect of the agents according to the invention in comparison to the known agents.

409837/1093

«Μ

• ϊ

H O

ιΗ

H O ■ Ρ

bO

. . τί a

• Η O

OS W

I Means according to the invention

0) ■ Ρ CO

Φ CO

CD

φ W) φ

(Q

CQ Ü

• 3

cd (Q

Φ 3

ο

ft

cd ο φ ο Q C

«J
ο

(β
• Η

Sl
• Ρ
O)

CO

Methyl N- [2- (Nn-buty1-N-pheny1-carbamoyloxy) phenyl) carbamate

Ethy 1-N - (> (Nn-buty1-N-pheny 1- carbamoyloxy) -phenyl) -carbamate

κ methyl-N- (3- (N-isobutyl-N-phenyl-I a carbamoyloxy) phenyl) carbamate

°? 5 methyl-N- (3- (N-isobutyl-N-

^ fΞ (3-methylphenyl) carbamoyloxy) - ^ ₃ I ₅ . phenyl) carbamate

f I

f I

Ξ I ethyl-N- (5- (N-isobutyl-N- (3-

- * "s methylphenyl) carbamoyloxy") - ⁰ a phenyl) carbamate ι-ι

I S-methyl-N- (5- (N-isobutyl-NI (5-methylpheny1) -carbamoyloxy) -? Phenyl) -thiocarbamate α φ

(Q P Oj

(β 4h • H

m as

-H bO • Η

.P

CO

io io oooooo ooo ooo

10 10 000 000 000 000

10 10 000 000 000 000

io- ooo ooo ooo ooo

10 10 000 000 000 00 0

10 10 000 000 000 000

OO

CD CD

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uqjsg

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PI P Ct

• IS ID "

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P et p Μ

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P! «RMue |« | »H! M OUO μ» Χ ■ uuetutH uaBinr-tucH: pu * l «» A

Η ¹ Ι

O S Ct "O CO Ctt3 03 OX OS

ΡΦ tr tr ι rr tr ι ρ et ρ β

►Jet H-OS H- Φ S * ip [ »let

o'er ο ρ α> ο ρ φ

§ «<ο ^ et ο« 5 et

Η «P H-CT PHtT

ο ι * i o «< * ι ό <<

«<25 Ο * Ρ M O * P

OVjI

Il Il

ΦΙ Φ O

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et I

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is

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I.

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ν »·

P ^ 1 3 0 * 55 ρ ρ 1

"1

VjI

before

• o c

? 4

Η ^^ Ό H- Ό I

O SS CTB O ^- O

3η- 5S §?

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tre im it Φ et οι O2J

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ctl- · I

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O O O O O O O O O O O O M. O O O O O O O I. O O O O O O O O O O I. I. O - O O O O O O O O O O O O O O O O O O O O O O O O M. O 0- O O O O O O O O O O O I. I. O I.

OVONIdiHOS

-CX-

ρ: to Φ

et et φ

Application rate kg active ingredient / ha

cotton Peanut

Polygonum lapathifolium

Stellaria media Senecio vulgaris

Lamium amplexicaule Centaure cyanus

Amarantus retroflexus

Chrysanthemum segetum Ipomoea purpurea

Echinochloa crus galli Setaria italica

Digitaria sanguinalis Setaria faberi

• Means according to the invention

(J) W

SS

• Η

α)

α)

• Η

5 W

(Q

if

ε α

a I

fat)

CU

• Η

(β O

(β

■ Ρ • Η

CO

• Η

Methyl N- (J- (N-n-buty1-N- (4-ethylphenyloarbamoyloxy) phenyl) carbamate

J 10 10 O

, S-methyl-N- (3- (N-benzyl-N-I I phenyl) carbamoyloxy) phenyl) thiols ϊ carbamate 3 10 10 0

Sf? Ethyl-N- (3- (N-benzyl-N-phenylco m I carbamoyloxy) phenyl) carbamate

OD I *

^w i ί V er bleach

->. = I N- (3-trifluoromethylphenyl) -N, N-
- * ^a S dimethy! urea

3 10 10 0.

3 010

Methyl N- (3- (N- (3-methylphenyl) -I carbamoyloxy) -phenyl) -carbamate 3528

I 10 = not damaged
0 = totally destroyed

(Q

CD

«Rl

■ Η

bO

CtJ • Η

OT

Patent department

February 28, 1973

Example 2

In the greenhouse, plants in the youth stage were treated with application rates of 2 kg active ingredient / ha, the agents in Form of aqueous emulsions with 500 liters of water / ha were used. The evaluation was carried out in the same way as the previous one Example 14 days after the treatment by scoring.

Even at this application rate, the agents according to the invention still have an outstanding herbicidal action.

ο α! αϊ

Ή + 3 + 3

ε C al al al

d «j <D ιΗ .ρ

W> O iH · Η

co O ^ H al Ή al al

-C C> »fc. ο X ο

\ rl (Ο φ -Η φ -H

φ * HO, C rH +3 χ)

bO <M co Φ OF ₄ al C

CO Q. ν ή η

Φ -P (O al> f-i

E 03 3 E ο cH φ

xiü 43 3 as al φ C

CkG -H rH .HO -H

U +3 +> CTj 43 3

Oj β ^ i 43 43 φ

Means according to the invention jjff jj ^ ^ | |

Methyl N- (3-fN-n-butyl-N-phenylcarbamoyloxy) phenyl) carbamate 2 0 0 0 0

Ethyl N- (3- (N-n-butyl-N-phenylcarbamoylQxy) -phenyl) -carbamate 2 0 0 0 0

0 = totally destroyed
10 = not damaged

Telex: t BI 777a echb d ■ Telegrams: Scheringchemie Berti · -15 - Post check KoMo: Berlin-West 11 75

409837/1093

Claims (1)

Patent claims ¹ I-NH - CO - X - in the R, propyl, butyl, isobutyl or benzyl, Rg phenyl or one or more times by methyl and / or Ethyl and / or chlorine and / or methoxy and / or methyl mercapto substituted phenyl, R, methyl or ethyl and X oxygen or sulfur mean. 2 · methyl N- (3- (N-n-butyl-N-phenylcarbamoyloxy) phenyl) carbamate. JJ. Ethyl N- (5- (N-n-butyl-N-phenylcarbamoyloxy) -phenyl) -carbaraate. ^. Methyl-N-Cj-CN-isobutyl-N-phenylcarbamoyloxy) -phenyl) -carbamate. 5 · Ethyl-N-C 1-4 -iN-isobutyl-N-phenylcarbamoyloxyJ-phenyl) -carbamate. 6. S-methyl-N- (3- (N-isbbutyl-N- (5-methylphenyl) carbamoyloxy) phenyl) thiocarbamate. Tele «: 181777» schb d · Telegrams: Scheringchemie Berlin - PosHcheck-Koolo : Berlin Wes «11 75 - 1D - ^ 098/17/1093 - * - SCHERINGAG 7. S-methyl-N- (3- (N-isobutyl-N-phenylcarbamoyloxy) -iAienyl) -thiocarbamate 8. S-methyl-N-O-CN-n-butyl-N-phenyl) -thiocarbamate. 9 · Methyl N- (3- (N-propyl-N-phei ^ learbamoylaxy) -phenyl) -carbamate. 10. Ethyl N- (3- (N-propyl-N- | * ienylcarbamoylQxy) -i * ienyl) -carbamate. 11. S-methyl-N- (3- (M-propyl-N-phenylcarbamoyloxy) -phenyl) -thiocarbarate. 12. Selective herbicidal agents based on diurethanes, characterized in that they contain at least one compound of the general formula 0 - CO - -NH - CO - X - in the R. Propyl, Butyl, Isobutyl or Benzyl, R _{2 is} phenyl or one or more times by methyl and / or Ethyl and / or chlorine and / or methoxy and / or Methyl mercapto substituted phenyl, R ^ methyl or ethyl and X oxygen or sulfur mean. -KmMo: Berfa-Wtal " 409837/1093 - * γ- SCHEFÖNGAG Patent department 231 06 A 9 February 28, 1973 15 · Selective herbicidal agents according to claim 12, characterized by a content of methyl-N- (j5- (N-n-butyl-N-phenylcarbamoyloxy ) -phenyl) -carbamate, ethyl-N- (3- (N-n-butyl-N-phenylcarbamoyloxy) -phenyl) -carbamate, Methyl N- (j5- (N-isobutyl-N-phenylcarbamoyleaqr) -phenyl) -carbamate, Ethyl N- (3- (N-isobutyl-N-phenylcarbamoyloxy) -pheny1) -carbamate, S-methyl-N- (3- (N-isobutyl-N- (3-methylphenyl) carbaraoyloxy) phenyl) thiocarbamate S-methyl-M-C ^ -iN-isobutyl-N-phenylcarbamoyl- <ay) -phenyl) -thiocarbamate, S-methyl-N- (3- (N-n-butyl-N-phenylcarbamoyloxy) -phenyl) -thiocarbamate, Methyl-N- (3- (N-propyl-N-phenylcarbamoyloxy) -phenyl ) carbamate, ethyl N- (3- (N-propyl-N-phenylcarbamoyloxy) -phenyl) -carbamate or S-methyl-N- (3- (N-propyl-N-phenylcarbamoyloxy) -phenyl) -thiocarbamate. 14. Selective herbicides according to claims 12 and I3 for use in building wool, carrot, peanut and rice crops. 15. Selective herbicides according to claims 12 to 14 for use post-emergence. 16. Process for the preparation of compounds of the general formula O - CO - : 181 777 * schb d - telegrams: Scheringchemie Beriia _Q 409837/1093 -λ- SCHERINGAG Patent department - 2310649 February 28, 1973 in the R. Propyl, Butyl, Isobutyl or Benzyl, R _{2 is} phenyl or one or more times through methyl and / or ethyl and / or chlorine and / or methoxy and / or methyl mercapto substituted phenyl, R, methyl or ethyl and X oxygen or sulfur mean, characterized in that a) compounds of the general formula ,. ¹ J-NH -CO-X- or their alkali salts with carbamoyl chlorides of the general formula ^Rl \ ^ N - CO - Cl optionally can react in the presence of a tertiary organic base or b) Compounds of the general formula 0 - CO - Cl CO - X - R Telei: I BI 777 «» chb d ■ Telegrams: Scheringchemie Berlin PoslscliecVKonto: Berlin-West Il 75 409837/1093 - »- SCHERINGAG »* OOinC / Q patent department -V »* I 6 IU b 4 y February 28, 1975 with amines of the general formula reacts in the presence of an acid acceptor or c) Compounds of the general formula 0 - CO catalytically hydrogenated to the corresponding amine and then with compounds of the general formula R, - X - CO - Cl
5 in the presence of an acid acceptor to the desired Reacts process products and then isolated them in the usual way, where R ,, Rg, R-, and X the above Have meaning. Board of Directors: Hans-JOrgen Hamann ■ Karl Otto Mitteletenscheid Telex: 181 777a «chb d ■ Telograms: Scheringchemie Berlin Dr. Gerhard Raspe Dr. Horst Witiel _. . “-. ·.», .. ». 8MIv .: Dr. Christian Bruhn Dr. Heim Hannse Postscheck account: Berlin-West 11 7β Chairman of the Supervisory Board: Dr. Eduard v. Schwartzkoppen · nODII ι < n «« Commercial register: AG Charlottenburg 93 HRB 283 and AG Kamen 5 HRB 71